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961.
Felix Houard Dr. Quentin Evrard Dr. Guillaume Calvez Dr. Yan Suffren Dr. Carole Daiguebonne Prof. Olivier Guillou Dr. Frédéric Gendron Dr. Boris Le Guennic Thierry Guizouarn Dr. Vincent Dorcet Prof. Matteo Mannini Dr. Kevin Bernot 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(2):790-794
We report a single-chain magnet (SCM) made of a terbium(III) building block and a nitronyl-nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long-range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self-organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each TbIII ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite-size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (Hc=2400 Oe MR=2.09 μB at 0.5 K) for this class of compounds. 相似文献
962.
Dr. Stéphanie Norsikian Dr. Cedric Tresse Dr. Marc François-Eude Dr. Louis Jeanne-Julien Dr. Guillaume Masson Vincent Servajean Dr. Grégory Genta-Jouve Prof. Jean-Marie Beau Dr. Emmanuel Roulland 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(16):6674-6678
A total synthesis of tiacumicin B, a natural macrolide whose remarkable antibiotic properties are used to treat severe intestinal infections, is reported. The strategy is in part based on the prior synthesis of the tiacumicin B aglycone, and on the decisive use of sulfoxides as anomeric leaving groups in hydrogen-bond-mediated aglycone delivery (HAD). This new HAD variant permitted highly β-selective rhamnosylation and noviosylation. To increase convergence, the rhamnosylated C1–C3 fragment thus obtained was anchored to the C4–C19 aglycone fragment by adapting the Suzuki–Miyaura cross-coupling used for the aglycone synthesis. Ring-size-selective macrolactonization provided a compound engaged directly in the noviolysation step with virtually total β selectivity. The final efficient removal of all the protecting groups provided synthetic tiacumicin B. 相似文献
963.
Van Elslande E Guérineau V Thirioux V Richard G Richardin P Laprévote O Hussler G Walter P 《Analytical and bioanalytical chemistry》2008,390(7):1873-1879
Microsamples of pink cosmetic powders from the Greco–Roman period were analyzed using two complementary analytical approaches
for identification of the colouring agents (lake pigments originally manufactured from madder plants with an inert binder,
usually a metallic salt) present in the samples. The first technique was a methanolic acidic extraction of the archaeological
samples with an additional ethyl acetate extraction of the anthraquinone-type colouring agents which were identified using
high performance liquid chromatography coupled to electrospray ionization with high resolution mass spectrometry (LC–ESI–HRMS),
and the second was direct analysis of a microsample by laser desorption ionization–mass spectrometry (LDI–MS). The latter
technique is well suited when the quantity of samples is very low. This soft ionization technique enables the detection of
very small quantities of compounds using the combination of positive and negative-ion modes. It was also successfully applied
for the direct analysis of some laboratory-made reference compounds. However, the presence of lead in one of these ancient
samples induced a spectral suppression phenomenon. In this case and conditional on a sufficient quantity of available sample,
the former method is better adapted for the characterization of these anthraquinone-type molecules. This study also confirmed
that purpurin, munjistin, and pseudopurpurin are the principal colouring agents present in these ancient cosmetic powders
constituted from madder plants.
Presented at the Annual French National Symposium on Mass Spectrometry, Electrophoresis and Proteomics, 20–23 September 2007
in Pau, France. 相似文献
964.
Selloum Djamel Techer Vincent Henni Abdellah Tingry Sophie Cretin Marc Innocent Christophe 《Journal of Solid State Electrochemistry》2020,24(3):623-631
Journal of Solid State Electrochemistry - Biofuel cells are an attractive alternative to conventional fuel cells, because they use biological catalysts. We report in this article the construction... 相似文献
965.
Jiaxin Tian Yan Chen Dr. Marie Vayer Alexandre Djurovic Régis Guillot Dr. Refka Guermazi Dr. Samuel Dagorne Dr. Christophe Bour Prof. Vincent Gandon 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(56):12831-12838
The catalytic activity of cationic NHC-ZnII and NHC-AlIII (NHC=N-heterocyclic carbene) complexes in reactions that require the electrophilic activation of soft C−C π bonds has been studied. The former proved able to act as a soft π-Lewis acid in a variety of transformations. The benefit of the bulky IPr NHC ligand was demonstrated by comparison with simple ZnX2 salts. The tested NHC-AlIII catalyst is not able to activate C−C π bonds but simple AlX2+ ions were found potent in some cases. 相似文献
966.
Robert J. Messinger Tan Vu Huynh Renaud Bouchet Vincent Sarou-Kanian Michaël Deschamps 《Magnetic resonance in chemistry : MRC》2020,58(11):1118-1129
Magic-angle-spinning (MAS) enhances sensitivity and resolution in solid-state nuclear magnetic resonance (NMR) measurements. MAS is obtained by aerodynamic levitation and drive of a rotor, which results in large centrifugal forces that may affect the physical state of soft materials, such as polymers, and subsequent solid-state NMR measurements. Here, we investigate the effects of MAS on the solid-state NMR measurements of a polymer electrolyte for lithium-ion battery applications, poly(ethylene oxide) (PEO) doped with the lithium salt LiTFSI. We show that MAS induces local chain ordering, which manifests itself as characteristic lineshapes with doublet-like splittings in subsequent solid-state 1 H, 7 Li, and 19 F static NMR spectra characterizing the PEO chains and solvated ions. MAS results in distributions of stresses and hence local chain orientations within the rotor, yielding distributions in the local magnetic susceptibility tensor that give rise to the observed NMR anisotropy and lineshapes. The effects of MAS were investigated on solid-state 7 Li and 19 F pulsed-field-gradient (PFG) diffusion and 7Li longitudinal relaxation NMR measurements. Activation energies for ion diffusion were affected modestly by MAS. 7Li longitudinal relaxation rates, which are sensitive to lithium-ion dynamics in the nanosecond regime, were essentially unchanged by MAS. We recommend that NMR researchers studying soft polymeric materials use only the spin rates necessary to achieve the desired enhancements in sensitivity and resolution, as well as acquire static NMR spectra after MAS experiments to reveal any signs of stress-induced local ordering. 相似文献
967.
Michael R. Keenan Vincent S. Smentkowski James A. Ohlhausen Paul G. Kotula 《Surface and interface analysis : SIA》2008,40(2):97-106
ToF‐SIMS spectra are formed by bombarding a surface with a pulse of primary ions and detecting the resultant ionized surface species using a time‐of‐flight mass spectrometer. Typically, the detector is a time‐to‐digital converter. Once an ion is detected using such detectors, the detector becomes insensitive to the arrival of additional ions for a period termed as the (detector) dead‐time. Under commonly used ToF‐SIMS data acquisition conditions, the time interval over which ions arising from a single chemical species reach the detector is on the order of the detector dead‐time. Thus, only the first ion reaching the detector at any given mass is counted. The event registered by the data acquisition system, then, is the arrival of one or more ions at the detector. This behavior causes ToF‐SIMS data to violate, in the general case, the assumption of linear additivity that underlies many multivariate statistical analysis techniques. In this article, we show that high‐mass‐resolution ToF‐SIMS spectral‐image data follow a generalized linear model, and we propose a data transformation and scaling procedure that enables such data sets to be successfully analyzed using standard methods of multivariate image analysis. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
968.
G. Kalaiarasi G. Aswini S. Rex Jeya Rajkumar S. Dharani Vincent M. Lynch R. Prabhakaran 《应用有机金属化学》2018,32(9)
Four different mononuclear palladium(II) complexes of 3‐acetyl‐8‐methoxycoumarin Schiff bases were synthesized and characterized by spectrochemical techniques. Further analysis through X‐ray crystallography confirmed the structures of the complexes. Their interactive ability with Calf Thymus DNA and protein (Bovine Serum Albumin and Human Serum Albumin) were investigated by means of absorption and emission methods. The intercalative mode of binding with DNA was supported by EB displacement studies and viscosity measurements. Configurational changes that occurred in the proteins have been analysed with the help of 3D fluorescence studies. The complexes were shown to have good antimicrobial activity against the tested bacterial and fungal pathogens. In addition, antiproliferative activity of the complexes was evaluated on A549 and MCF‐7 cell lines and the complexes were comparatively more active than the standard drug cisplatin. Among the compounds, complex 3 was the most effective against MCF‐7 (IC50 value of 5.20 ± 0.15 μM) and A549 (5.09 ± 0.13 μM) compared with the other complexes 1 (6.48 ± 0.17 μM; 5.98 ± 0.09 μM), 2 (5.53 ± 0.12 μM; 5.85 ± 0.11 μM), 4 (6.73 ± 0.19 μM; 6.63 ± 0.16 μM) and cisplatin (16.79 ± 0.08 μM; 15.10 ± 0.05 μM) respectively. LDH and NO release assays confirmed the cytotoxic potential of the synthesized complexes. 相似文献
969.
2-Ethoxy-3,4-dihydro-2H-pyran-6-carbonitriles are obtained in high yield by stereospecific endo-mode cyclo-additions of α,β-unsaturated acyl cyanides and ethyl vinyl ether at room temperature. The nitrile group is converted to some other functionalities. 相似文献
970.
Dr. Janis V. Musso Vincent Gramm Sarjano Stein Dr. Wolfgang Frey Prof. Dr. Michael R. Buchmeiser 《欧洲无机化学杂志》2023,26(3):e202200649
A series of molybdenum alkylidyne silyloxy N-heterocyclic carbene (NHC) complexes of the general formula [Mo(≡C(R))(OSiPh3)3(NHC)] (R=tBu, 4-methoxyphenyl, 2,4,6-trimethylphenyl; NHC = 1,3-diisopropylimidazol-2-ylidene, 1,3-dicyclohexylimidazol-2-ylidene, 1,3-dicyclohexyl-4,5-dihydroimidazol-2-ylidene, 1,3-dimethylimidazol-2-ylidene, 1,3-dimethyl-4,5-dichloroimidazol-2-ylidene) was synthesized. Single crystal X-ray analyses revealed that with increasing steric demand of the alkylidyne group, enhanced air-stability of the complexes in the solid-state is achieved with the most stable complex (R=2,4,6-trimethylphenyl, NHC = 1,3-diisopropylimidazol-2-ylidene) being stable in air for 24 h without showing signs of decomposition in 1H NMR. In contrast to previously reported air-stable molybdenum-based complexes, the novel catalysts proved to be highly active in alkyne metathesis, allowing for turnover numbers (TONs) of up to 6000 without further activation, and tolerant towards several functional groups such as tosyl, ether, ester, thioether and nitro moieties. Their air stability allows for facile handling of the catalysts in air and even after exposure to ambient atmosphere for one week, the most stable representative still displayed high productivity in alkyne metathesis. 相似文献